JPS61275128A - Synthesized fraipontite type mineral and its production - Google Patents

Abstract

PURPOSE:To increase the degree of whiteness and a make the specific surface area large by incorporating crystalline SiO2, Zn component and Al component in a prescribed proportional and subjecting the mixture to the hydrothermal reaction in the presence of a crystallization accelerator to make it a prescribed crystalline structure. CONSTITUTION:Crystalline SiO2, Zn component consisting of ZnO and Zn(OH)2 or a Zn compd. capable of forming Zn(OH)2 and Al component consisting of Al2O3 hydrate, Al(OH)3 or an Al compd. capable of producing these are prepared. These three components are blended so that the component consisting of 5-45mol% SiO2, 35-65mol% ZnO and 2-60mol% Al2O3 is obtained and the mixture is subjected to the hhydrothermal reaction. A synthesized fraipontite mineral which has a X-ray diffracted image shown in a table by measuring it with Cu-K, by 2theta<=0.5 half value width of three strong interference lines, the laminated platy crystal, >=80% brightness by Hunger and >=10m<2>/g specific surface area is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Use The present invention relates to a synthetic flybontite g mineral and a method for synthesizing the same. This article relates to a synthetic flypontite mineral having laminated plate-like crystals and a method for synthesizing the same.

The conventional technology fraipontitt is based on the formula F
3ZnO-2Al, 03-55 i 0. '11H
It has a chemical composition expressed by 0, and is known as a mineral that has a crust made of fibrous crystals, is yellowish white, has a muntine luster, and is similar to asbestos.
This mineral is said to have an unknown origin, although it is said that the amount was extracted from the mine of GG, but as far as the present inventors know, there is no known example of its successful synthesis to date.

Outline and Purpose of the Invention The present inventors selected crystalline silica such as cristopalite as a silica raw material, and treated it with a zinc component and an aluminum component in the coexistence of a salt of a basic nitrogen compound and an acid. When performing a hydrothermal reaction, X-ray diffraction reveals a well-developed flybontite crystal structure, excellent whiteness, a large specific surface area despite well-developed crystals, and a synthetic mineral with laminated plate-like crystals. was found to be obtained.

An object of the present invention is to provide a synthetic mineral with a well-developed flypontite crystal structure and a method for producing the same.

Another object of the present invention is to provide a new synthetic mineral of the flybontite type, which has excellent whiteness, a relatively large specific surface area, and has laminated plate-like crystals, and a method for producing the same.

Still another object of the present invention is to provide a method for producing synthetic flybontite minerals from readily available raw materials without requiring any particular troublesome operations.

Structure of the Invention According to the present invention, Cu- has an X-ray diffraction image measured by α and represented by the following Table 7 100 24-2660 66-3540 37-3930 44-4610 59-6120 It has a diffraction image that is substantially the same as that of the X-ray diffraction image, and the half-value widths of the three strong lines in the X-ray diffraction image are all 0.5 degrees or less at 2θ. A synthetic flybontite mineral comprising aluminum-containing zinc phyllosilicate having a specific surface area of nVf or more is provided.

According to the present invention, furthermore, (α) crystalline silica, Cb) zinc white, zinc hydroxide, or a zinc compound capable of producing zinc hydroxide under reaction conditions, and (c) alumina hydrate, aluminum hydroxide, or reaction The aluminira present compound capable of producing these under the conditions, expressed as an oxide, has a three-component composition ratio of 5 t Ot 5 to 45 molt, Zoo 35 to 6
5 molti and At, 0. A method for synthesizing a synthetic flybontite mineral is provided, which is characterized by carrying out a hydrothermal reaction in a quantitative ratio corresponding to 2 to 60 molar and in the presence of a salt of a basic nitrogen-containing compound and an acid.

In this specification, the salt of a basic nitrogen-containing compound and an acid means an acid addition salt to a basic nitrogen compound or a salt produced by neutralizing the compound and an acid.

Preferred embodiments of the invention The present invention will be explained in detail below.

1) Structure and characteristics of synthetic flybontite The synthetic flybontite according to the present invention is mainly composed of zinc phyllosilicate or aluminum-containing zinc phyllosilicate with a two-layer structure, and consists of a tetrahedral layer of SiO4 and an octahedral layer of ZnO6. The basic skeleton is a two-layer structure in which the facepiece layer and the facepiece layer are combined in a layered manner.
A part of the Si of the 5in4 tetrahedron is replaced with AI, and corresponding to this parens, a part of the Z of the octahedron of Zn06 is also replaced with At.

The basic chemical structure of this synthetic flypontite is given by the following formula (1), where X is 0.1 to 1.75, particularly 0.
The value is between 6 and 1.0.

Naturally occurring flybontite has an X value of approximately 0.6
5, whereas in the present invention, X
It is clear that the value of can be varied over a fairly wide range.

In the synthesis of flybontite, crystalline synthetic flybontite is most likely to be produced within the range of the above-mentioned compositional formula, especially in a composition close to that of natural flybontite, but the three-component composition ratio expressed as an oxide is S i O.

5-45 mol%, Zn035-65 mol%, and Al2
When the O32 to 60 molar ratio is in the range, a phyllosilicate mineral having a flybontite crystal structure can be obtained.

FIG. 1 of the accompanying drawings shows an X-ray diffraction image of a synthetic mineral according to the invention. From this drawing, it can be seen that the synthetic mineral according to the present invention has an extremely well-developed flybontite crystal structure. The synthetic mineral according to the present invention exhibits an X-ray diffraction image that is substantially the same as the X-ray diffraction image shown in Table 7, where "substantially the same" means that the relative intensity of each peak is ±15
This means that it can vary within the range of . The degree of development of the crystal structure, that is, the uniformity or regularity of the interplanar spacing, can be evaluated by the half-width. In the synthetic mineral according to the present invention, the half-value widths of the three strong lines in the X-ray diffraction image shown in Table 7 are all 0.5 degrees or less in 2θ, and the regularity of the interplanar spacing is excellent.

For reference, the X-ray diffraction image of naturally occurring 7-libontite is as shown in Table 8 below according to the 4STM card of 1974.

8th surface spacing tt x (A) Relative intensity I/I07
, 00 100 3.52 70 2.63 30 2.48 20 2.33 20 2.25 10 2.12 10 1.99 10 1, 76 10 1.65 10 1, 53 20 The synthetic minerals according to the present invention are as follows. Measured by the method of 6
It has a crystallinity of 0% or more, especially 70% or more.

Method for Measuring Crystallinity (a) Determine the X-ray diffraction curve of the sample by powder X-ray diffraction method using α rays for Cu-.

(b) Points corresponding to 20=10° and 2θ=63° of the diffraction curve are connected with a straight line to form a baseline. Furthermore, 2θ=
If the point corresponding to 10° is located above the lowest point between 20=10 and 20°, then this lowest point and 2
A straight line connects the point at θ: 66° to form the baseline. Also, the points corresponding to 2θ = 63° are 20 = 50 to 63
Even if it lies above the lowest point between the two, this lowest point is taken to form the baseline.

(c) The amorphous line is formed by connecting the lowest point between the valleys of adjacent diffraction peaks (excluding those where the distance between the tails of the diffraction peaks is less than 1°) Base line and amorphous line The area between the lines is SA,
The area between the amorphous line and the diffraction curve is defined as Sc, and the degree of crystallinity (%) is determined by the following formula.

The synthetic mineral according to the invention generally consists of laminated plate crystals. FIG. 2 of the accompanying drawings is an electron micrograph showing the particle structure of the synthetic mineral obtained in Example 1, which will be described later. This photograph shows that the synthetic mineral of the present invention has a structure in which plate-shaped crystallites are laminated in multiple layers. As mentioned above, naturally occurring 7-libontite is composed of fibrous crystals, whereas
It is recognized that the two are significantly different in that the crystal of the present invention is a laminated plate crystal.

The synthetic minerals according to the invention have an exceptionally high specific surface while having a very well-developed crystal structure. That is, a highly crystalline inorganic substance with a degree of crystallinity of 60 or more generally has a specific surface area of 10rr? /f, whereas the synthetic minerals according to the present invention generally have a
Especially from 40 to 180 n? /? Shows the specific surface area of

Also, this flybontite mineral is a synthetic product.

It does not contain impurities that cause coloration and is finely crystalline, and has excellent whiteness, with a Hunter whiteness of 8(]1% or more, especially 90% or more). In particular, the synthesis method according to the present invention uses oxides, hydroxides, etc. as raw materials, and has the advantage of being substantially free of contaminant ions.

The particle size of this synthetic flybontite varies over a wide range, and generally speaking, the median size measured by centrifugal sedimentation is 0.
．． It is in the range of 1 to 20 μm, especially 1 to 10 μm.

This synthetic flybontite mineral is generally obtained in a fairly bulky state, and its oil absorption is generally 50 d/10 C1 or more, particularly within the range of 80 to 180 m/100 t,
Is its bulk density 0.2 to 0.6? /CC within range.

11) Synthesis method The present invention has a synthetic advantage in that crystalline silica such as cristopalite is used as a silicic acid raw material and a hydrothermal reaction is carried out in the presence of a salt of a basic nitrogen-containing compound and an acid. This is a book with the following characteristics. That is, the hydrothermal reaction in the presence of the above salts has the effect of developing a crystal structure, but
When crystalline silica is used as a silica raw material, a flypontite mineral with a higher degree of crystallinity can be obtained than when amorphous silica is used.

Various types of crystalline silica are known, including quartz, cristopalite, and tridymite.
Any of these may be used, but cristopalite is particularly preferred. The crystalline silica may be natural or synthetic; for example, natural cristopalite or synthetic cristopalite obtained by calcining diatomaceous earth or synthetic amorphous silica can be used for the purposes of the present invention. be done.

Another feature of the method of the present invention is that other raw materials can also be used in the form of oxides or hydroxides.

As the zinc component, zinc white and zinc hydroxide are preferably used. Of course, it is also possible to hydrolyze a water-soluble zinc salt such as zinc chloride, zinc nitrate, zinc sulfate, etc., and use fresh zinc hydroxide just generated in the reaction. Of course, the above hydroxide may be formed in the reaction system and subjected to the reaction.

As the aluminum component, alumina hydrate and aluminum hydroxide are preferably used. There are various theories regarding the distinction between alumina hydrate and aluminum hydroxide, but in this specification, those that exhibit characteristic absorption of hydroxyl groups by infrared absorption spectrometry are referred to as aluminum hydroxide, and those that exhibit broad absorption due to the presence of water. Those in which only alumina is recognized are called alumina hydrate. Examples of alumina hydrate or aluminum hydroxide include 41 (OH)s boehmite 2 such as gibbsite and payerite, and A such as diasbore.
10-OH, boehmite gel (hydration degree 1.5-2.0)
etc. are used. In addition, amorphous aluminum hydroxide can of course also be used for the purpose of the present invention. Furthermore, aluminum compounds that can be easily dihydrolyzed in the reaction system, such as aluminum alkoxides, can also be used for the purpose of the present invention.

Instead of subjecting the above-mentioned six components to hydrothermal treatment, it is also possible to generate in advance a two-component amorphous composite oxide or hydroxide or coprecipitate of zinc component and aluminum component and use this in the reaction. can.

The usage ratio of the three components or the three component oxide standard composition ratio is si
o, 5 to 45 mol%, especially 20 to 40 mol%, Zn
O35 to 65 mol, especially 45 to 60 mol, At
, 03'l to 60 molti, particularly preferably 5 to 30 molti.

In the present invention, when a salt of a basic nitrogen-containing compound and an acid is coexisting in the reaction system, the crystal structure is well developed even though the above-mentioned raw materials are used. Minerals are formed.

The basic nitrogen-containing compound is an inorganic or organic compound containing a nitrogen atom in the form of ammonium, amine, hydrazine, or guanidine, and is used in the form of a neutralized salt with an acid or an acid addition salt. A basic nitrogen-containing compound that is not in the form of a salt shows almost no effect of promoting crystallization into the flybontite structure.

Examples are shown below, but the present invention is of course not limited to these.

Ammonium salts of inorganic or organic acids such as ammono sulfate, ammono nitrate, ammono chloride, ammono phosphate, ammono acetate, and ammono propionate.

Acid addition salts of amine type primary, secondary or 6th class amines, such as mono-, di- or triethanolamine, hydrochloride, mono-, di- or triethylamine hydrochloride addition salt, morpholine, pyridine, piperazine, piperidine, aniline・Hydrochloride, mono- or sialin ・hydrochloride, ethylenediamine ・hydrochloride salt, etc.

Hydrazine type hydrazine hydrochloride, methylhydrazine hydrochloride, hydrazine hydrochloride, etc.

Guanidine type guanidine hydrochloride, guanidine phosphate 0 Among these, mineral acid ammonium salts such as ammonium sulfate and ammonium chloride are preferred because they are easily available and inexpensive.

These basic nitrogen-containing compounds are preferably present in an amount of 10 to 300 molti, especially 20 to 150 molti per zinc component. In the present invention, the reason why the presence of a basic nitrogen-containing compound efficiently generates a flybontite crystal structure during hydrothermal treatment has not yet been elucidated, but the basic nitrogen-containing compound is used as a raw material for zinc. It is presumed that this is due to the formation of a complex compound that facilitates the formation of ZnO and octahedral layers during this process.

During hydrothermal synthesis, the concentration of solids in the aqueous slurry is not particularly limited, but it is desirable from the viewpoint of workability and economy that it be 6 to 30% by weight, particularly 5 to 201% by weight. The conditions for hydrothermal synthesis are generally a temperature of 110 to 300 C, particularly 140 to 200 C, and a temperature of 0.5
9/i (gauge) to 87, especially 2.5 to 15/-
(gauge) pressure, and the reaction time is
Under the above conditions, 6 to 24 hours is generally sufficient.

The obtained product is separated from the mother liquor (1), washed with water, and dried if necessary to obtain a product. Incidentally, since the separated mother liquor contains substantially only basic nitrogen-containing compounds, it can be reused for the next reaction.

Applications The synthetic flybontite according to the invention has properties as a solid acid due to the fact that it is composed of aluminum-containing zinc phyllosilicate. Also, this material has a specific surface area of 2
It has a high surface activity of 0 yr/S' or more, and has excellent whiteness.

Due to these properties, the product according to the invention exhibits significantly better coloring performance when in contact with various leuco dyes,
It can be advantageously used as a color developer for pressure-sensitive paper or as an auxiliary agent for organic color developer.

The synthetic flybontite according to the present invention further comprises acidic S
i04 Since it is based on a two-layer structure in which a tetrahedral layer and a basic ZnO and octahedral layer are combined, it has the surprising property of adsorbing both basic dyes and acidic dyes. has. Utilizing this characteristic, the synthetic mineral having a synthetic flybontite structure according to the present invention can be advantageously used for forming an ink receiving layer of an inkjet recording medium.

The invention is illustrated by the following example.

Test method The test method for each item in this specification is as follows.1.
, counting device 5071) was used.

The diffraction conditions are as follows.

Target Cu Filter Ki Detector SC Voltage 35 KVP Current 15m, 4 counts, full scale
10.000 C/1 Time constant 1 sec Scanning speed 2°/- Chart speed 2 cm/1m Radiation angle
1 degree slit width 0.3 brightness angle 6 degrees 2 Hunter brightness In this example, an automatic reflectometer TR-600 manufactured by Tokyo Denshoku ■ was used.

3. BET specific surface area [S, , 4) The specific surface area of each powder is the so-called BE due to adsorption of nitrogen gas.
It was measured according to the T method. For details, please refer to the following literature.

S, Brunauer, P, H, Emmett,
E. Te1ler.

/, Am, Chgm, Sot, VoL 6[
], 309 (1938) In this specification, the specific surface area is measured by drying it in advance to 150C, placing it in a 0.5-0.6f weighing bottle, drying it for 1 hour in a constant temperature dryer at 150C, and immediately Weigh the weight accurately. This sample was placed in an adsorption sample tube, heated to 200C, and degassed until the degree of vacuum within the adsorption sample tube reached 10-'ymHt.
After cooling, the adsorption sample tube was placed in liquid nitrogen at about -1960℃, and P? '/l/P' = 0.05-0.30 (pH
7: Nitrogen gas pressure, po = atmospheric pressure at specific time of measurement) between 4 and
5 points Measure the amount of gas adsorbed. Then, the amount of nitrogen gas adsorption after subtracting the dead volume is converted to the amount of adsorption at 11 atmospheres DC and substituted into the BET equation, Fm[CC/1] (Nitrogen gas adsorption required to form a monomolecular layer on the sample surface) amount),
seek. Specific surface area S, A = 4.35 x Vm
Crr? /f) Example 1: Take ammonium chloride 165' (0.3 mol) in a 1 t beaker and add water to make a 0.6 t aqueous solution.

Here, diatom ± (cristopalite type silica, manufactured by Showa Kagaku Kogyo ■) 12f (SiO, min: 0.2 mol), zinc oxide 24 f (0.3 mol) and boehmite gel 1
Add 4t (At, o, min: 0.1 mol) and stir. Put this slurry into a 1 ton autoclave container,
A hydrothermal synthesis reaction was carried out at 180C for 6 hours under stirring conditions of 300 rpm. After cooling, the reaction mass was taken out, filtered with suction, washed with water and dried at 110C. The obtained dry cake was pulverized using a sample mill, and coarse particles were removed by elutriation to obtain a white powder.

In this way, a flypontite aluminum-containing zinc phyllosilicate having a two-layer structure was obtained.

Example 2 Acidic clay from Hosoetsudo, Higashikanbara District, Niigata Prefecture (contains about 60% cristopalite and about 2 g of quallon on a dry matter basis) was crushed (moisture 35 elb) and IKf was mixed with 3 to 4 parts of 25% sulfuric acid. was added, heated at 95C for 10 hours, and treated with P once to remove the treatment solution, then 6 noodles of 25% sulfuric acid were added again, and heated at 95C for 10 hours to carry out acid treatment. A cake was obtained by filtration and washing with water. The resulting cake was placed in a bot mill, water was added, and it was wet-milled with silica sand (Kuorutsu).The upper suspension was discarded six times using a wood block, and a slurry containing 10% of Sin was obtained from the remaining precipitate. Ta.

Next, add 20? of ammonium sulfate to a 1 ton beaker.
Take (0.15 mol) and add water to make a 0.61 aqueous solution. The obtained 10 silica slurry (contains about 80% cristopalite and about 3% quartz in total silica) 120? (Sin 2 min 0.2 mol), zinc oxide 24
P (0.3 mol) and aluminum hydroxide (Hisilite H-42M, manufactured by Showa Light Metal Co., Ltd., 16 tCO, 0.2 mol) are added and stirred. This slurry was placed in a 1 ton autoclave container and stirred at 300 rpm at 180C.
A hydrothermal synthesis reaction was carried out for 6 hours. After cooling, the reaction was removed, filtered with suction, washed with water and dried at 110c.

After pulverizing the obtained dry cake using a sample mill,
Coarse particles were removed by elutriation to obtain a white powder. In this way, a flypontite aluminum-containing zinc phyllosilicate having a two-layer structure was obtained.

Example 3: The same procedure as in Example 1 was carried out except that the hydrothermal reaction conditions (180C for 6 hours in Example 1) were changed to 20DC for 24 hours.Thus, it had a two-layer structure. A flypontite type aluminium-containing zinc phyllosilicate was obtained.

The Hunter whiteness, specific surface area, and X-ray diffraction analysis results of the powders obtained in Examples 1 to 2 are listed in Table 1.

Table 1

[Brief explanation of the drawing]

Fig. 1 is an X-ray diffraction spectrum of a flybontite type aluminium-containing zinc phyllosilicate mineral according to Example 1 of the present invention, which is based on α-rays in Cu-. This is a scanning deaf electron micrograph (magnification: 20.000 times) showing the particle structure of a flypontite-type aluminum-containing zinc phyllosilicate mineral.

Claims (3)

[Claims] (1) Measured with Cu-Kα and the following plane spacing (2θ) ￥ ￥ relative intensity (I/I_o) ￥ 11-14 100 24-26 60 33-35 40 37-39 30 44-46 10 59-61 It has a diffraction image that is substantially the same as the X-ray diffraction image represented by % or more and a specific surface area of 10 m^2/g or more. (2) (α) Crystalline silica, (b) Zinc white, zinc hydroxide, or a zinc compound capable of producing zinc hydroxide under reaction conditions, and (c) Alumina hydrate, aluminum hydroxide, or under reaction conditions. SiO_2
5-45 mol%, ZnO35-65 mol% and Al_2
1. A method for synthesizing a synthetic flypontite mineral, which is characterized by carrying out a hydrothermal reaction in a quantitative ratio corresponding to O_32 to 60 mol% and in the presence of a salt of a basic nitrogen-containing compound and an acid. (3) The method according to claim 2, wherein the crystalline silica is cristoparite type silica.